Meso-selective synthesis of ansa-metallocenes

Abstract

The present invention relates to a process for the meso-selective preparation of ansa-metallocene complexes of the formula (I), which comprises reacting a ligand starting compound of the formula (II) with a transition metal compound of the formula III, where R 1 , R 1 are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms, R 2 , R 2 are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms, R 3 is a bulky organic radical which has at least 3 carbon atoms, is bound to the oxygen atom via a nonaromatic carbon or silicon atom and may be substituted by halogen atoms or further organic radicals having from 1 to 20 carbon atoms and may also contain heteroatoms selected from the group consisting of Si, N, P, O and S, T, T′ are identical or different and are each a divalent organic group which has from 1 to 40 carbon atoms and together with the cyclopentadienyl ring forms at least one further saturated or unsaturated, substituted or unsubstituted ring system having a ring size of from 5 to 12 atoms, where T and T′ may contain the heteroatoms Si, Ge, N, P, As, Sb, O, S, Se or Te within the ring system fused to the cyclopentadienyl ring, A is a bridge consisting of a divalent atom or a divalent group, M 1 is an element of group 3, 4, 5 or 6 of the Periodic Table of the Elements or the lanthanides, the radicals X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion, x is a natural number from 1 to 4, M 2 is an alkali metal, an alkaline earth metal or a magnesium monohalide fragment, p is 1 in the case of doubly positively charged metal ions or 2 in the case of singly positively charged metal ions or metal ion fragments, LB is an uncharged Lewis base ligand, and y is a natural number from 0 to 6, and also the subsequent reaction of these complexes to form ansa-metallocenes of the formula (IV), the use of transition metal compounds of the formula (III) for preparing metallocenes and also transition metal compounds of the formula (III), ansa-metallocene complexes of the formula (I) and the use of these as constituents of catalyst systems for the polymerization of olefines.

1. A process for meso-selective preparation of ansa-metallocene complexes of formula (I): 
       
         
           
           
               
               
           
         
       
       which comprises reacting a ligand starting compound of formula (II): 
       
         
           
           
               
               
           
         
       
       with a transition metal compound of formula (III):
   (LB) y M 1 (OR 3 )X x+1   (III) 
 
       where
 R 1 , R 1′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
 R 2 , R 2′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
 R 3  is a bulky organic radical comprising at least 3 carbon atoms, and is bound to the oxygen atom via a nonaromatic carbon or silicon atom, and may be substituted by halogen atoms or further organic radicals comprising from 1 to 20 carbon atoms, and optionally comprise at least one heteroatom selected from the group consisting of Si, N, P, O and S; 
 T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te; 
 A is a bridge consisting of a divalent atom or a divalent group; 
 M 1  is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements; 
 X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion; 
 x is a natural number from 1 to 4; 
 M 2  is an alkali metal, an alkaline earth metal, or a magnesium monohalide fragment; 
 p is 1 when M 2  is a doubly positively charged metal ion, or 2 when M 2  is a singly positively charged metal ion or metal ion fragment; 
 LB is an uncharged Lewis base ligand; 
 and 
 y is a natural number from 0 to 6. 
 
     
     
       2. The process as claimed in  claim 1 , wherein an ansa-metallocene complex of formula (I) is converted into an ansa-metallocene complex of formula (IV): 
       
         
           
           
               
               
           
         
       
       where
 R 1 , R 1′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
 R 2 , R 2′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
 T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te; 
 A is a bridge consisting of a divalent atom or a divalent group; 
 M 1  is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements; 
 X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion; and 
 x is a natural number from 1 to 4; 
 
       comprising reacting the ansa-metallocene complexes of formula (I) with at least one suitable elimination reagent in a subsequent reaction step. 
     
     
       3. The process as claimed in  claim 1 , wherein
 R 1 , R 1′  are identical or different and are each a C 1 -C 10 -alkyl; 
 R 2 , R 2′  are each hydrogen; 
 T, T′ are identical or different and are each an unsubstituted 1,3-butadiene-1,4-diyl group or a 1,3-butadiene-1,4-diyl group substituted with from 1 to 4 R 4  radicals, where R 4  can be identical or different and are organic radicals having from 1 to 40 carbon atoms; and 
 A is ethylene, substituted ethylene or substituted silylene. 
 
     
     
       4. The process as claimed in  claim 2 , wherein
 R 1 , R 1′  are identical or different and are each a C 1 -C 10 -alkyl; 
 R 2 , R 2′  are each hydrogen; 
 T, T′ are identical or different and are each an unsubstituted 1,3-butadiene-1,4-diyl group or a 1,3-butadiene-1,4-diyl group substituted with from 1 to 4 R 4  radicals, where R 4  can be identical or different and are organic radicals having from 1 to 40 carbon atoms; and 
 A is ethylene, substituted ethylene or substituted silylene. 
 
     
     
       5. The process as claimed in  claim 1 , wherein
 R 3  is an alkyl radical branched in an α position, and comprises from 4 to 40 carbon atoms, and is optionally substituted by at least one halogen atom or organic radical comprising from 1 to 10 carbon atoms; 
 M 1  is Ti, Zr or Hf; 
 X is halogen; 
 x is 2; 
 LB is a cyclic or acyclic ether or diether; 
 and 
 y is 1 or 2. 
 
     
     
       6. The process as claimed in  claim 2 , wherein
 R 3  is an alkyl radical branched in an α position, and comprises from 4 to 40 carbon atoms, and is optionally substituted by at least one halogen atom or organic radical comprising from 1 to 10 carbon atoms; 
 M 1  is Ti, Zr or Hf; 
 X is halogen; 
 x is 2; 
 LB is a cyclic or acyclic ether or diether; 
 and 
 y is 1 or 2. 
 
     
     
       7. The process as claimed in  claim 1 , wherein
 M 2  is Li, Na, K, MgCl, MgBr, MgI or Mg. 
 
     
     
       8. The process as claimed in  claim 2 , wherein
 M 2  is Li, Na, K, MgCl, MgBr, MgI or Mg. 
 
     
     
       9. A method for preparing ansa-metallocene complexes comprising reacting a metallocene complex with a transition metal compound of formula (III):
   (LB) y M 1 (OR 3 )X X+1   (III). 
 
     
     
       10. A transition metal compound of the formula (III):
   (LB) y M 1 (OR 3 )X X+1   (III) 
 where 
 R 3  is a bulky organic radical comprising at least 3 carbon atoms, and is bound to the oxygen atom via a nonaromatic carbon or silicon atom, and may be substituted by halogen atoms or further organic radicals comprising from 1 to 20 carbon atoms, and optionally comprise at least one heteroatom selected from the group consisting of Si, N, P, O and S; 
 M 1  is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements; 
 X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion; 
 x is a natural number from 1 to 4; 
 LB is an uncharged Lewis base ligand; 
 and 
 y is a natural number from 0 to 6. 
 
     
     
       11. A method for preparing ansa-metallocene complexes of formula (IV) as set forth in  claim 2  comprising reacting a metallocene complex of formula (I): 
       
         
           
           
               
               
           
         
         where 
         R 1 , R 1′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
         R 2 , R 2′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
         R 3  is a bulky organic radical comprising at least 3 carbon atoms, and is bound to the oxygen atom via a nonaromatic carbon or silicon atom, and may be substituted by halogen atoms or further organic radicals comprising from 1 to 20 carbon atoms, and optionally comprise at least one heteroatom selected from the group consisting of Si, N, P, O and S; 
         T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te; 
         A is a bridge consisting of a divalent atom or a divalent group; 
         M 1  is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements; 
         X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion; and 
         x is a natural number from 1 to 4; 
       
       with a transition metal compound. 
     
     
       12. An ansa-metallocene complex of formula (I): 
       
         
           
           
               
               
           
         
         where 
         R 1 , R 1′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
         R 2 , R 2′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
         T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te; 
         A is a bridge consisting of a divalent atom or a divalent group; 
         R 3  is an alkyl radical branched in an α position, and comprises from 4 to 40 carbon atoms, and is optionally substituted by at least one halogen atom or organic radical comprising from 1 to 10 carbon atoms; 
         M 1  is Ti, Zr or Hf; 
         X is halogen; and 
         x is 2. 
       
     
     
       13. A constituent of a catalyst system for polymerizing at least one olefin comprising an ansa-metallocene complex of formula (I): 
       
         
           
           
               
               
           
         
         R 1 , R 1′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
         R 2 , R 2′  are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms; 
         R 3  is an alkyl radical branched in an α position, and comprises from 4 to 40 carbon atoms, and is optionally substituted by at least one halogen atom or organic radical comprising from 1 to 10 carbon atoms; 
         T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te; 
         A is a bridge consisting of a divalent atom or a divalent group; 
         M 1  is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements; 
         X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion; and 
         x is a natural number from 1 to 4.